EP3362435A1 - Composés, polymères et formulations de revêtement comprenant au moins un précurseur de n-halamine, un centre cationique et un groupe d'incorporation au revêtement - Google Patents

Composés, polymères et formulations de revêtement comprenant au moins un précurseur de n-halamine, un centre cationique et un groupe d'incorporation au revêtement

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Publication number
EP3362435A1
EP3362435A1 EP16854689.3A EP16854689A EP3362435A1 EP 3362435 A1 EP3362435 A1 EP 3362435A1 EP 16854689 A EP16854689 A EP 16854689A EP 3362435 A1 EP3362435 A1 EP 3362435A1
Authority
EP
European Patent Office
Prior art keywords
group
coating
polymer
cyclic
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16854689.3A
Other languages
German (de)
English (en)
Other versions
EP3362435A4 (fr
Inventor
Zachary J. WOLFF
Sadegh GHANBAR
Dominic Tessier
Chenxi NING
Jonathan VAN LEEUWEN
Marcelo DUBIEL
Gurmeet Singh BINDRA
Song Liu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Manitoba
Original Assignee
Exigence Technologies Inc
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Filing date
Publication date
Application filed by Exigence Technologies Inc filed Critical Exigence Technologies Inc
Publication of EP3362435A1 publication Critical patent/EP3362435A1/fr
Publication of EP3362435A4 publication Critical patent/EP3362435A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/56—Nitrogen atoms
    • C07D211/58—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C07D233/78—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • This disclosure generally relates to compounds having biocidal properties and/or a potential for increased biocidal properties.
  • This disclosure also relates to coating formulations comprising said compounds.
  • the coating formulations are for coating substrates to provide biocidal properties and/or a potential for increased biocidal properties to the coated substrates.
  • this disclosure relates to coating formulations with at least one compound that comprises an N-halamine precursor group, at least one cationic center, and a coating-incorporation group.
  • Microorganisms such as bacteria, archaea, yeast or fungi, can cause disease, spoilage of inventory, process inefficiencies, disruptions of healthy natural environments and infrastructure degradation. More specifically, healthcare-associated infections (HAIs) are a serious and growing challenge to health care systems around the world. HAIs cause over 100,000 deaths annually and have become the 3 rd leading cause of death in Canada. It is estimated that in any given year, HAIs directly cost the United States healthcare system between about $30B and about $45B. Added to this challenge is the increasing prevalence of microorganisms that are resistant to currently available antimicrobial intervention products and processes, including preventative approaches (disinfectants used to control environmental contamination) and reactive approaches (remedies including the use of antibiotics). Therefore, it is necessary to deploy biocidal technologies in various environments as a strategy for controlling unwanted levels or types of micro-organisms.
  • HAIs healthcare-associated infections
  • a common approach for disinfecting of both hard and soft surfaces is the use of liquid disinfectants. Selection of a suitable disinfectant for any given application is dependent upon the environment where the disinfectant will be applied. Selection criteria include the types of micro-organisms targeted, contact time for the disinfectant, level of toxicity tolerable in each application, cleanliness (or lack thereof) of the surface to be cleaned, sensitivity of the surface materials to oxidization (i.e., leading to corrosion of the substrate), the presence or absence of biofilms, the amount of organic load present on substrate surfaces, and local regulations that may restrict the use of certain active ingredients within a disinfectant. Some environments are far more challenging to adequately disinfect than others.
  • UNDER ARMOUR ® Under Armour registered trademark of Under Armour, Inc. markets a Scent Control technology that comprises a blend of at least silver and zinc.
  • the biocidal activity of these silver-incorporated textiles is limited by the amount of silver that is present and available to react with micro-organisms. The amount of silver is finite and may decrease as the textiles are laundered. It is also known to modify textiles that incorporate polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the PAM-PET composite fabric demonstrated close to a 6-log reduction of all the tested bacteria. Furthermore, the N-chloramine on the PAM-PET was evaluated. After 29 regeneration cycles, the PAM-PET (active chlorine 306 ppm) was still able to provide 6-log reduction of HA-MRSA (isolate #70527) within 20 minutes of contact.
  • International patent application number PCT/CA2013/000491 teaches using forming a semi-interpenetrating network upon a PET surface. The network provides at least one alkynyl group for covalently bonding cyclic amide, azido-5, 5-dimethyl-hydantoin (ADMH).
  • the surface coating may have biocidal activity or it may have a potential for biocidal activity when activated with subsequent treatment step.
  • the chemistry of the coating formulations of the present disclosure allow standard industrial processes to be used for applying the coating formulation to a substrate in a minimal amount of time to increase the cost effectiveness of the application process.
  • At least one further component that is selected from a group that includes at least: acetate polymers, vinyl ester polymers including vinyl acetate polymers, vinyl acetate homopolymers, acrylate polymers including methacrylate polymers, melamines, modified melamines, urethane polymers, polyurethane polymers, aliphatic urethane polymers, polyesters, self-crosslinking polyesters, epoxide polymers including epoxide-ester polymers, fluoropolymers, silicone or silicone derivative polymers, polyethylene, polypropylene, polyvinyl chloride, polyamides, polybutylene, poly(buta-l,3-diene), polysulfone, or combinations thereof; and
  • a compound that may be selected from a group of compounds that have an alkenyl monomer that comprises at least one N-halamine precursor and at least one quaternary ammonium moiety.
  • a compound is provided that is selected from a group of compounds that have the general formula [I] :
  • the N-halamine is a cyclic halamine or an acyclic N-halamine, when the N-halamine is cyclic then Zi , QUATi and Li are nil (or absent);
  • Li and L 2 are each independently a linker which can be a Ci-C 2 o alkyl, a cyclic aromatic, a non-aromatic ring, ether, ketone, or any other organic linking structure;
  • QUATi has general formula:
  • QUAT 2 has a general formula:
  • Ri and R 2 are each independently a Ci-Ce alkyl or a Ci-Ce alkyl that terminates in a cyclic aromatic group with between 3 and 8 carbons or a cyclic non-aromatic group with between 3 and 8 carbons;
  • L3 is nil (absent) or a linker which can be one of a Ci-C 2 o alkyl; a cyclic aromatic, a non-aromatic ring, ether, ketone, or any other organic linking structure;
  • X " is one of F " , Br “ , CI “ or ⁇ ;
  • A is one of R3, cyclic N-halamine, acyclic N-halamine or -N ⁇ RsRe;
  • R3 is nil (absent) or one of a C1-C20 alkyl; a cyclic aromatic group, a cyclic non- aromatic group, ether, ketone, or any other organic linking structure;
  • R.4 and R5 are each independently a Ci-Ce alkyl or a Ci-Ce alkyl that terminates in a cyclic aromatic group with between 3 and 8 carbons or a cyclic non-aromatic group with between 3 and 8 carbons;
  • Zi and Z 2 are each independently selected from a group consisting of a direct bond (i.e., Zi and/or Z 2 are absent or nil), a coating-incorporation group (CIG) that is selected from a group consisting of the following functional groups: an alcohol; a primary amine; a secondary amine; a tertiary amine; an ether; an epoxide; a carbonyl group and derivatives thereof such as an acyl, an aldehyde, a ketone, a carboxylic acid, an anhydride, an ester, an amide; an alkyl halide, such as a vinyl chloride, a vinyl fluoride; a vinyl group and derivatives thereof, such as a vinyl acetate and a methyl methacrylate, a vinyl-pyridine, a vinyl-benzylidene; an isocyanate group; a carboxyl group and an associated carboxylate ion; a thiol; a phenol group
  • the CIG may be a branching group that may branch into an aliphatic alkane, alkene or alkyne-chain that is terminated with one or more functional groups.
  • Another embodiment of the present disclosure relates to a compound that is selected from a group of compounds having one of the general formulas [II] through [XXIII], wherein X " may be selected from any one of F " , Br, CI " or P:
  • the coating formulation comprises at least one further component that is a polymer selected from a group that includes at least: acetate polymers, vinyl ester polymers including vinyl acetate polymers, vinyl acetate homopolymers, acrylate polymers including methacrylate polymers, melamines, modified melamines, urethane polymers, polyurethane polymers, aliphatic urethane polymers, polyesters, self-crosslinking polyesters, epoxide polymers including epoxide-ester polymers, fluoropolymers, silicone or silicone derivative polymers, polyethylene, polypropylene, polyvinyl chloride, polyamides, polybutylene, poly(buta-l,3-diene), polysulfone, or combinations thereof.
  • the coating formulation also comprises a compound that comprises at least one N-halamine precursor, at least one quaternary ammonium moiety and a CIG.
  • a substrate comprising at least one surface that is coated with a coating formulation that comprises a polymer selected from a group that includes at least one of: acetate polymers, vinyl ester polymers including vinyl acetate polymers, vinyl acetate homopolymers, acrylate polymers including methacrylate polymers, melamines, modified melamines, urethane polymers, polyurethane polymers, aliphatic urethane polymers, polyesters, self-crosslinking polyesters, epoxide polymers including epoxide-ester polymers, fluoropolymers, silicone or silicone derivative polymers, polyethylene, polypropylene, polyvinyl chloride, polyamides, polybutylene, poly(buta-l,3-diene), polysulfone, or combinations thereof.
  • the coating formulation also comprises a compound that is selected from a group of compounds that comprise an N- halamine precursor, at least one quaternary ammonium moiety and a CIG
  • FIG. 1 is a schematic representation of a chemical reaction for synthesizing a compound of the present disclosure
  • FIG. 2A, FIG. 2B, FIG. 2C, FIG. 2D, FIG. 2E, 2F, 2G and 2H are each schematic representations of chemical reactions for synthesizing further compounds of the present disclosure
  • FIG. 3A, FIG. 3B, FIG. 3C, FIG. 3D, FIG. 3E, 3F and 3G are each schematic representations of chemical reactions for synthesizing further compounds of the present disclosure
  • FIG. 4 is a schematic representation of a coating system according to an embodiment of the present disclosure.
  • FIG. 5A is a photograph of a further coating system according to the present disclosure.
  • FIG. 5B is a photograph of an example of processing equipment for use in the coating system depicted in FIG. 4 or FIG. 5A;
  • FIG. 6 is a schematic representation of another example of a coating system
  • FIG. 7 is a line graph that depicts representative chlorination data obtained from substrates coated in coating formulations of the present disclosure after a number of chlorine washes;
  • FIG. 8 is a line graph that depicts representative re-chlorination data obtained from substrates coated with coating formulations of the present disclosure after a number of chlorine washes
  • FIG. 9 is a line graph that depicts representative active surface chlorine levels data obtained from substrates coated in coating formulations of the present disclosure after different numbers of wash cycles
  • FIG. 10A and FIG. 10B are both line graphs that depict representative biocidal activity data obtained from substrates coated in coating formulations of the present disclosure and other modified textiles that were exposed to Methicillin-resistant Staphylococcus aureus (MRSA);
  • FIG. 11A and FIG. 11B are both line graphs that depict representative biocidal activity data obtained from a substrate coated in a coating formulation of the present disclosure, over time;
  • Some embodiments of the present disclosure relate to one or more compounds that can be incorporated into a coating formulation for coating onto a substrate.
  • the coated substrate may have biocidal activity or the potential for increased biocidal activity.
  • the potential for increased biocidal activity may be realized by exposing the substrate to one or more additional agents, such as one or more halogens.
  • Some embodiments of the present disclosure relate to one or more coating formulations that comprise a compound that may be in the form of a monomer.
  • the compound comprises at least (i) one or more cationic centers, (ii) an N-halamine precursor group, and (iii) at least one coating-incorporation group (CIG).
  • the CIG may react with another component of the coating formulation or with a component of a substrate or both.
  • the N-halamine precursor group is at least one of imidazolidine-2, 4-dione (hydantoin); 5, 5- dimethylhydantoin; 4, 4-dimethyl-2-oxazalidione; tetramethyl-2-imidazolidione; 2, 2, 5, 5- tetramethylimidazo-lidin-4-one; a uracil derivative; piperidine or combinations thereof.
  • the N-halamine precursor group may be converted into an N-halamine by a halogenation reaction whereby at least one of the hydrogens present on the N-halamine precursor group is replaced by a halogen atom, such as a chlorine, a bromine or an iodine atom.
  • the halogen atom replaces a hydrogen of the N-halamine precursor group that is bonded to a nitrogen atom also of the N-halamine precursor group.
  • the replacement reaction may be an addition reaction or some other reaction mechanism.
  • the compound may be incorporated into a thermoplastic-polymer system that may be synthesized through methods such as those described above or others including additional processing. Additionally, processing of the thermoplastic polymer system may include, but is not limited to: extrusion; co-extrusion; molding; thermoforming; calendaring; compounding; thermoforming or other process may be used to coat or integrate the compound into or onto a base polymer-matrix.
  • the compound may be incorporated into a thermosetting-polymer system or a polymeric precursor thereto that may be processed as described above.
  • processing of the thermoplastic-polymer system and precursors may include, but is not limited to: reaction injection molding or other forming or coating processes, which may or may not involve an addition of a catalyst or other reactive chemistries.
  • coating formulations comprising a compound disclosed herein and at least one further component. The compound may be covalently bonded to the at least one further component, or not.
  • the coating formulation may further comprise a component that acts as a crosslinking agent.
  • a CIG of a compound when present it is present it may incorporate the compound into a polymer within a coating formulation.
  • the CIG when the CIG is: • a mono-amine, the CIG may be useful for chain growth polymerization into epoxy or polyurethane systems;
  • the CIG may allow for curing into epoxy systems through a crosslinking mechanism
  • the CIG may allow for curing into epoxy or polyurethane systems through a crosslinking mechanism
  • the CIG may be used to tether molecules to epoxide groups present on a surface, as long as a competitive curing process is not taking place at the same time;
  • the CIG may react into polyurethane polymers through chain growth polymerization and during a cure within a crosslinking reaction;
  • the CIG may react with various base polymers such as vinyl or silicone-based systems in the presence of a modified melamine crosslinker through a step-growth polymerization process;
  • the CIG may react with ester groups in most any polymer backbone through a step-growth polymerization process
  • the CIG may homopolymerize to form acrylic or acrylate polymers, or be copolymerized with other moieties to also form vinyl or latex thermoplastic polymers;
  • a polymer matrix may be achieved through radical polymerization. Forming a thermoset matrix via chain growth;
  • a polymer matrix may be achieved through radical polymerization. Forming a thermoset matrix via chain growth;
  • an alkene or vinyl group which can homopolymerize to form a polyolefin polymer, or be copolymerized with other moieties to form polyethylene, polypropylene, polybutylene, poly(vinyl chloride), or other thermoplastic polymers through an addition polymerization process, or a radical polymerization process;
  • an alkene or vinyl group which can be co-polymerized with other moieties including but not limited to perfluorocycloalkene, ethylene, vinyl fluoride, vinylidene fluoride (1, 1-difluoroethylene), tetrafluoroethylene, chlorotrifluoroethylene, propylene, hexafluoropropylene, perfluoropropylvinylether and perfluoromethylvinylether to form a fluoropolymer through an addition polymerization process, a radical polymerization process, or other polymerization method.
  • the coating formulation may be coated onto one or more surfaces of the substrate by, for example, a coating process that comprises a step of wetting the substrate surface with a liquid that comprises the coating formulation and a drying step to dry the coated substrate.
  • a coating process that comprises a step of wetting the substrate surface with a liquid that comprises the coating formulation and a drying step to dry the coated substrate.
  • the dried coated-substrate may then be subjected to a subsequent curing step.
  • Suitable substrates include textiles, metal, metal alloys, polymers, ceramic, glass, natural substances, such as wood, a combinations thereof, and the like.
  • the textiles may be natural, synthetic or combinations thereof.
  • the term “activity” refers to biocidal activity.
  • biocide refers to a chemical compound, a chemical composition or a chemical formulation that can kill or render harmless one or more microbes.
  • coating formulation refers to a chemical composition that can be used to coat a substrate, where the chemical composition made may be a mixture of different chemical components that undergo one or more chemical reactions to form a coating upon a substrate.
  • N-halamine refers to a compound containing one or more nitrogen-halogen covalent bonds that is normally formed by the halogenation of imide, amide or amine groups of a compound. The presence of the halogen renders the compound biocidal.
  • N-halamines as referred to in the present disclosure, include both cyclic and acyclic N- halamine compounds.
  • N-halamine precursor and ""N-halamine precursor group” may be used synonymously and can be any N-H, preferably with the absence of an alpha hydrogen, as part of either a cyclic or acyclic organic structure.
  • These functional groups may contain one or more nitrogen-hydrogen bonds that can be converted into a one or more nitrogen-halogen bonds normally formed by the halogenation of imide, amide or amine groups of the functional group.
  • the presence of the halogen may convert an N-halamine precursor into an N-halamine, which may render the functional group biocidal.
  • quaternary ammonium cation As used herein, the terms “quaternary ammonium cation”, “quaternary ammonium compound”, “quaternary ammonium salt”, “QAC”, and “quat” may be used interchangeably throughout the present disclosure to refer to ammonium compounds in which four organic groups are linked to a nitrogen atom that produces a positively charged ion (cation) of the structure NR4 + .
  • organic linker-group includes at least the following functional groups phenyl, propane, butane, pentane, hexane, cyclic propane, cyclic butane, cyclic pentane or cyclic hexane.
  • Ri and R2 are each independently a Ci-Ce alkyl or a Ci-Ce alkyl that terminates in a cyclic aromatic group with between 3 and 8 carbons or a cyclic non-aromatic group with between 3 and 8 carbons;
  • L3 is nil (absent) or a linker which can be one of a C1-C20 alkyl; a cyclic aromatic, a non-aromatic ring, ether, ketone, or any other organic linking structure;
  • A is one of R3, cyclic N-halamine, acyclic N-halamine or -N ⁇ RsRe;
  • R3 is nil (absent) or one of a C1-C20 alkyl; a cyclic aromatic group, a cyclic non- aromatic group, ether, ketone, or any other organic linking structure; R4 and R5 are each independently a C1-C6 alkyl or a C1-C6 alkyl that terminates in a cyclic aromatic group with between 3 and 8 carbons or a cyclic non-aromatic group with between 3 and 8 carbons;
  • the CIG may be a branching group that may branch into an aliphatic alkane, alkene or alkyne-chain that is terminated with one or more functional groups.
  • the compounds or precursor compounds are derivatized to allow attachment of the compound or precursor to another compound(s) or surface or substrate or polymer.
  • the compounds or precursors disclosed herein may be derivatized to include an azide moiety or an alkynyl group to allow for attachment to another compound(s) or surface or substrate or polymer through "click" chemistry.
  • the compound is synthesized by the reaction depicted in FIG. 1 and the compound has the general formula (XXV), wherein X " is one of Br " , CI " or ⁇ :
  • AS1 Coating Formulation 1
  • AS2 Coating Formulation 2
  • AS3 Coating Formulation 3
  • AS1 Coating Formulation 1
  • AS2 Coating Formulation 2
  • AS3 Coating Formulation 3
  • Table 1 provides the mass and % of total mass for the chemical components used to produce the Coating Formulation 1.
  • Table 2 provides the mass and % of total mass for the chemical components used to produce the Coating Formulation 2.
  • FIG. 3 depicts one coating system 10, which is not intended to be limiting, that may be used to coat a substrate 12 with any of the coating formulations of the present disclosure.
  • the substrate 12 may be flexible, such as a textile, or the substrate 12 may be rigid, such as an article made from any one of: a polymer, a metal, a metal alloy, a synthetic material, a material derived from nature or combinations thereof.
  • the substrate 12 may also be referred to as padding the substrate 12.
  • the coating system 10 comprises a padding mangle 14, a coating tank 16 and a dryer 18.
  • the coating tank 16 may also be referred to as a dip tank.
  • the substrate 12 may proceed through the coating system 10 as a continuous length of material so that one portion of the substrate 12 may be entering the coating system 10 while another portion of the same material may be a coated substrate 12A that is leaving the coating system 10.
  • the substrate 12 may be under tension while moving through the coating system 10.
  • the padding mangle 14 may comprise a first roller 14A, a tank roller 14B and a squeeze roller 14C.
  • the first roller 14A is positioned at an end of the coating system 10 that is opposite to the dryer 18.
  • the first roller 14A may define an entry point of the coating system 10 and the dryer 18 may define an exit point of the coating system 10.
  • the substrate 12 passes over the first roller 14A, the substrate is pulled into the coating tank 16 by the tank roller 14B.
  • the coating tank 16 holds a coating formulation 20 that will be coated onto the substrate 12 as it passes therethrough.
  • the coating formulation 20 may comprise any one of the coating formulations described herein.
  • the squeeze roller 14C causes the substrate 12 to turn a comer, exit the coating tank 16 and pass through the squeeze roller 14C.
  • the squeeze roller 14C may comprise two rollers that are aligned and spaced apart to allow the substrate 12 to pass through a gap that is defined between the two rollers.
  • the squeeze roller 14C removes excess coating formulation 20, which then falls back into the coating tank 16.
  • the distance between the two rollers of the squeeze roller 14C can be changed to increase or decrease a pressure that is applied to the substrate 12 as it passes through the squeeze roller 14C.
  • the pressure applied to the substrate 12 by the squeeze roller 14C may be referred to as a pad pressure.
  • the substrate 12 then passes through a dryer 18.
  • the coating system 20 may also include a curing stage 22, which follows the dryer 18.
  • the curing stage 22 may be a second, downstream section of the dryer 18 or the curing stage 22 may be a separate machine that forms part of the coating system 10.
  • FIG. 4 is a photograph of one example of the coating system 10, the padding mangle 14 and tank 16 is manufactured by Ernst Benz Ag, model KLF HU 500.
  • the rotor and roll size of this model are 4 cm and 10.5 cm, respectively.
  • the maximum volume of the coating tank is about 2 L.
  • Substrate material can be fed at a substantially constant rate of about 0.5 ml min.
  • the size of the substrate 12 samples can be about 30 cm x about 30 cm.
  • the maximum width of substrate 12 that can be accommodated by this apparatus is about 50 cm.
  • the substrate 12 is subjected to a coating process that comprises a step of pulling the uncoated substrate 12 around the first roller 14A and the tank roller 14B.
  • the uncoated substrate is dipped into the coating tank 16 that contains the coating formulation 20.
  • the substrate 12 is then pulled through the squeeze roller 14C wherein the substrate 12 is squeezed under pressure to remove excess coating formulation 20.
  • the wet pick-up is about 80% to about 100%.
  • the substrate 12 is then pulled into the dryer 18 where it is dried at about 105 °C for about 2 minutes to remove water from the coating formulation 20.
  • the substrate 12 may then move to the curing stage 22 where it is exposed to about 140 °C for about 2 minutes.
  • the higher temperatures of the curing stage 22 may promote the formation of crosslinking within the coating formulation 20, which may increase the durability of the coated substrate 12.
  • the coating system 10 performs the coating process described above.
  • the equipment that performs the coating process was selected for compatibility with existing industrial processes.
  • Previous methods that were developed to adhere antimicrobial compounds to a substrate 12 were found to rely on multi-stage processes that were likely to introduce enough cost to the manufacturing process to limit the economic feasibility of the disclosure to only certain markets and industries.
  • the coating system 10 and the coating process used in the present method can be directly scaled to industrial-scale textile finishing processes. A typical industrial set-up would have the same process flow as shown in FIG. 3.
  • the width of the substrate 12 for an industrial coating system 10 is likely to be about 2 meters with a common rate of substrate feeding of about 20 m/ min.
  • the dryer 18 and curing section 22 can be scaled to match the scale of the increased feed rate of the substrate 12.
  • the drying process may take place from about 100 °C to about 105 °C, and the curing process may occur between about 120 °C to about 170 °C.
  • the Coating Formulations 1, 2 and 3 were used as the coating formulation 20 within the coating system 10 to coat the substrate 12.
  • the substrate 12 is a textile that is a blend of natural and synthetic fibers, which may be referred to herein as polycotton, that has a ratio of about 65/35 of polyester/cotton (Item Code 7409-CFT, TestFabrics, Inc.).
  • polycotton which is a synthetic dominated blend, indicates that the coating formulations developed may adhere to other polymer substrates as well.
  • Table 4 provides the parameters of the coating system 10 for each of the Coating Formulations 1, 2 or 3, with Coating Formulation 3 being used under two different coating parameters. Table 4. Parameters used in the coating system with three coating formulations.
  • the padding mangle 14 has an arbitrary scale for pad pressure set between 0 and 10.
  • padding mangles allow the pad pressure to be set using one of PSI, N/m or Kpa as a unit of measure. In the coating system 10, the absolute pad pressure was not measured. Instead, the pad pressure was adjusted to achieve about 85% wet pickup.
  • the coated substrates 12A were characterized according to wet pickup %, dry pickup %, and by how much of the coating formulation was added to the substrate 12 as a weight % increase. This final parameter was calculated using the following general formula (IXX): (% antimicrobial salt in formulation * % wet pickup) / (100 + % dry pickup) (IXX).
  • the coating process described above may also be used to adhere a coating to other substrates, such as a polymer film 112.
  • a surfactant may be used to provide adequate wettability and spreading of the coating formulation, if desired, for coating various surfaces such as polyethylene terephthalate (PET) fibers, such as poly cotton, and PET films.
  • PET polyethylene terephthalate
  • FIG. 6 depicts an example of a coating system 100 that may be suitable for coating a polymer film 112.
  • the coating system 100 comprises a set of one or more rollers 114 and a coating tank 116.
  • the set of rollers may include at least one supporting rollers 114A, an upper roller 114B and a lower roller 114C.
  • the supporting rollers 114A support the polymer film 112 as it moves between the upper roller 114B and the lower roller 114C, which are positioned vertically opposite to each other.
  • one or more of the support rollers 114A, the upper roller 114B and the lower roller 114C may be motorized to move the polymer film 112 through the coating system 100.
  • Rotation of the upper and lower rollers 114B, 114C causes the lower roller 114C to dip into and apply the coating formulation 20 to a lower surface of the polymer film 112.
  • a compressive force is applied to the polymer film 112, which removes any undesired coating formulation 20 from the coated surface of the polymer film 112.
  • the polymer film 112 then moves along the supporting rollers 114C to a dryer and, optionally, to a curing stage.
  • the dryer and curing stage of system 100 may be similar to those described above for the coating system 10, or not.
  • the coating system 100 may be similar to, or the same as, a kiss-roll system that is used for finishing membranes.
  • the further component TRIBUILD DX-164 (Tri-Tex Co, Inc) is a homopolymer of polyvinyl acetate and TRICOMEL 100 (Tri-Tex Co, Inc) is a modified melamine which will crosslink almost any crosslinkable polymer such as carboxylated styrene butadiene, acrylic, polyvinyl acetate, polyvinyl chloride, amino functional silicone, and others.
  • TRIBUILD DX-164 and TRICOMEL 100 can react during the curing process to form a thin film of polymer coating on textile substrates.
  • the thin-film coating formulations may hold embedded antimicrobial compounds or precursors thereof in place.
  • the compounds described herein that are part of a Coating Formulation may be embedded, absorbed or trapped, inside the thin-film polymer coatings.
  • sufficient N-halamine groups may be available to bind, uptake, upload or otherwise bond to a chlorine atom from the local environment of the substrate's surface.
  • the further components RayCryl 1853 and RayFlex 683 are polyesters formed from the polymerization of acrylate esters. These further components have a good film-forming property and can adhere strongly to textile substrates. According to the technical notes of RayCryl 1853, this acrylic polymer may also self-crosslink to form a durable film coating.
  • the Coating Formulations 1, 2 and 3 were designed to covalently bond to polymer substrates. Multiple investigations have shown that the compound of Formula II may not be well-suited to physical incorporation into polymer matrixes due to its solubility in water, which is unlike most antimicrobial agents. Also, the compound is not intended to act as a leaching agent and, therefore, the coating process should permanently adhere the compound to the substrate 12. Typically, surface modification processes (a.k.a. priming) have previously been necessary to form covalent bonds between the compound and the substrate 12.
  • the binding agents selected for the Coating Formulations 1, 2 and 3 are useful as they may form a crosslinked thin-film polymer to physically incorporate or trap the molecular structure of the N-halamine and/or QUAT onto any surface.
  • the coating formulations and processes of the present disclosure may demonstrate how to reduce the finishing treatment from multiple processing steps requiring several hours to complete and hazardous working conditions, to a simpler, safer coating process that requires only minutes to perform.
  • FIG. 2 and FIG. 3 both depict example chemical reactions for synthesizing examples of a compound, which may also be referred to herein as a monomer or monomer compound. These examples of compounds may comprise an N-halamine, at least one quaternary ammonium moiety and a CIG. Certain further embodiments of the present disclosure are compounds having the following general formulae [II] through to [XXIII] :
  • Another embodiment of the present disclosure relates to a compound that is selected from a group of compounds that have one of the general formulas [II] through [XXII A], wherein X " may be selected from any one of F " , Br, CI " or P:
  • the one or more further components may provide heat curing, air curing or photo-curing properties to the coating formulation.
  • the coating formulations may comprise a thermoplastic polymer, a precursor or a prepolymer of a thermoplastic polymer, a thermoset polymer, a precursor or a prepolymer of a thermoset polymer or combinations thereof.
  • the coating formulations may comprise a polymer that is selected from a group that includes but is not limited to: acetate polymers, vinyl acetate polymers, vinyl acetate homopolymers, melamines, modified melamines, urethane polymers, aliphatic urethane polymers, polyesters, self- crosslinking polyesters, polyaryletherketone polymers, polyether ether ketone polymers or combinations thereof.
  • the coating formulations may comprise polyepoxides that may homopolymerize or may polymerize with one or more CIGs, such as but not limited to: polyfunctional amines, acids, acid anhydrides, phenols, alcohols, epoxides and thiols.
  • CIGs such as but not limited to: polyfunctional amines, acids, acid anhydrides, phenols, alcohols, epoxides and thiols.
  • the coating formulations may comprise a polymer that is selected from a group that includes at least acetate polymers, vinyl ester polymers including vinyl acetate polymers, vinyl acetate homopolymers, acrylate polymers including methacrylate polymers, melamines, modified melamines, urethane polymers, polyurethane polymers, aliphatic urethane polymers, polyesters, self-crosslinking polyesters, epoxide polymers including epoxide-ester polymers, fluoropolymers, silicone or silicone derivative polymers, polyethylene, polypropylene, polyvinyl chloride, polyamides, polybutylene, poly(buta-l,3-diene), polysulfone, or combinations thereof.
  • the coating formulation can form a thin-film polymer coating that comprises molecules of the compounds disclosed herein that are chemically incorporated into a polymer structure or that are embedded or trapped or otherwise chemically associated with a polymer structure of the coating formulation.
  • the further components for the coating formulations may be selected from a group of commercially available chemicals that includes but is not limited to: TRIBUILD DX-164 (Tri-Tex Co, Inc), TRICOMEL 100 (Tri-Tex Co, Inc), RAYCRYL ® 1853 (RAYCRYL is a registered trademark of Specialty Polymers Products, Inc.), RAYFLEX ® 683 (RAYFLEX is a registered trademark of Specialty Polymers Products, Inc.), or combinations thereof.
  • the coating formulations may also include water. These further components of the coating formulations provide the polymer system within each coating formulation. Each polymer system reacts, in some fashion, with a CIG to incorporate the compounds of the present disclosure into the polymer systems.
  • NCI Coating Formulation 4
  • NC2 Coating Formulation 5
  • NC3 Coating Formulation 6
  • NC4 Coating Formulation 7
  • NC5 Coating Formulation 8
  • NC6 Coating Formulation 9
  • Table 6 shows the mass and % of total mass for the chemical components used to produce the Coating Formulation 4.
  • Table 7 shows the mass and % of total mass for the chemical components used to produce the Coating Formulation 5.
  • Table 9 shows the mass and % of total mass for the chemical components used to produce the Coating Formulation 7.
  • Table 11 shows the mass and % of total mass for the chemical components used to produce the Coating Formulation 9.
  • the operational parameters of the coating system 10 for each of the Coating Formulations 4, 5, 6, 7, 8 and 9 were substantially the same with a pad speed of 0.5 meters/minute, a pad pressure of 5 (arbitrary scale between 1 and 10), a drying temperature of 105 °C, a drying time of 2 minutes, a curing temperature of 140 °C and a curing time of 2 minutes.
  • the substrate 12 used for these samples was polycotton.
  • the Coating Formulations 4, 5, 6, 7, 8 and 9 were evaluated in terms of wet and dry pickup, and absolute addition of the biocidal molecule or precursors thereof by weight % addition.
  • the coated samples were either not chlorinated, one-time chlorine washed, or 5- times chlorine washed. These coated samples were evaluated for chlorination propensity and durability of the coating formulations.
  • the different chlorine wash were performed according to the AATCC 188- 2010 test method, "Colorfastness to Sodium Hypochlorite Bleach in Home Launderings.”
  • the different chlorine wash provided data on the amount of active chlorine loading possible with the example coating formulations, and data relevant to the durability of the example coating formulations.
  • Table 13 below shows the wet pick-up, the dry pick-up, the antibacterial salt % measured in the various of coated substrates 12A that were coated with the Coating Formulations 4 through 9 with various degrees of chlorination.
  • the modified melamine in the TRICOMEL 100 can potentially react with the compounds within the coating formulations either via Michael addition or radical graft polymerization (a radical might be generated on melamine amines upon curing) to bond onto, or within, a thin-film polymer coating, which may result in a more durable coating on the substrate.
  • Michael addition or radical graft polymerization a radical might be generated on melamine amines upon curing
  • Further coating formulations for soft substrates were prepared.
  • the following further coating formulations may be suitable for coating a textile substrate, such as poly cotton.
  • Table 13A provides a summary of the further components of the further coating formulations described further below.
  • TRICOSIL® A silicone-based polymer coating pre-cursor.
  • TRIBUILD MB Modified polyvinyl acetate copolymer latex, contains no alkyl phenol NPF ethoxylates (APEO)
  • TRICOFRESH Modified self -catalyzed imidazolidinone, with low levels of fromaldehyde LOC
  • Catalyst 531 Aqueous magnesium chloride solution. Solution is a pH of 1.
  • RayCryl 1853 High solids acrylic emulsion polymer. Self crosslinking and carboxyl group.
  • Table 14 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 10.
  • Table 15 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 11.
  • Table 17 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 13.
  • Table 18 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 14.
  • Table 20 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 16.
  • Table 21 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 17.
  • Table 22 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 18.
  • Table 22 Chemical components used to produce the Coating Formulation 17A.
  • Table 23 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 18.
  • Table 24 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 19.
  • Table 25 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 20.
  • Table 25 Chemical components used to produce the Coating Formulation 20.
  • Table 26 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 21.
  • Table 27 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 22.
  • Table 28 shows a summary description of the commercially available components used as further components in the following hard-surface coating formulations. Table 28 Descri tion of Further Components in some Hard-Surface Coating Formulations.
  • the hard-surface coating formulations that include "*" were separately coated on to Nylon 66 plastic (food grade) and stainless steel 304.
  • the hard- surface coating formulations in Table 34 to Table 40 were coated on to Nylon 66 plastic (NN, food grade).
  • the components of the hard-surface coating formulations in Table 29 to 40 were mixed, coated on to a hard substrate with a hand foam roller and then heated with a heat gun for drying. When dried, the coated hard substrates were cured as indicated in the tables below.
  • Table 29 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 23.
  • Table 29 Chemical components used to produce the Coating Formulation 23.
  • Table 30 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 24.
  • Table 32 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 26.
  • Table 32 Chemical components used to produce the Coating Formulation 26.
  • Table 33 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 27.
  • Table 34 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 28.
  • Table 35 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 29.
  • Table 36 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 30.
  • Table 37 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 31.
  • Table 38 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 32.
  • Table 39 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 33.
  • Table 40 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 34.
  • the hard-surface coating formulations in Table 41 to Table 44 were coated on to Nylon 66 Plastic (NN, food grade) and acetal plastic (AL).
  • Table 41 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 35.
  • the components of the hard-surface coating formulations in Table 41 through Table 44 were mixed, coated on to a hard substrate with a hand foam roller and then dried at 102 °C and cured for 5 minutes at 140 °C.
  • Table 42 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 36.
  • Table 42 Chemical components used to produce the Coating Formulation 36.
  • Table 43 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 37.
  • Table 44 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 38.
  • Table 44 Chemical components used to produce the Coating Formulation 38.
  • the hard-surface coating formulations in Table 45 were coated on to a galvanized- steel substrate.
  • Table 45 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 39.
  • the components of Coating Formulation 39 were mixed, applied to a galvanized steel substrate with a hand-foam roller and dried with a heat gun. Multiple coats of the Coating Formulation 39 may have been applied after drying and before curing.
  • the Coating Formulation 39 was cured at 90 °C for 3 hours followed by a post-cure of 130 °C for 30 minutes.
  • Table 46 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 40.
  • Table 46 Chemical components used to produce the Coating Formulation 40.
  • Table 47 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 41.
  • Table 47 Chemical components used to produce the Coating Formulation 41.
  • Table 48 shows the mass and % of total mass for the chemical components used to produce a Coating Formulation 42.
  • Coated substrate samples were tested for chlorine loading propensity, chlorine loading kinetics, and for antibacterial efficacy. The effect of accelerated life cycles on durability was also investigated. This section describes the measurements of chlorination.
  • two commercially available sportswear textiles LULULEMON, SILVERSCENT product that incorporates the X- STATIC silver product and an UNDER ARMOUR product with Scent Control technology that comprises a blend of at least silver and zinc were tested.
  • a commercially available CLOROX® CLOROX is a registered trademark of The Clorox Company
  • Clorox N-chloramine
  • the concentration of active chlorine on the fabric samples was analyzed by a traditional iodometric titration method. Each l x l inch sample was immersed in a solution of 30 mL distilled water and 25 mL of 0.001N sodium thiosulfate standard solution. After stirring in a lOOmL beaker with a magnetic stir rod for 60 min, 2 mL of 5% acetic acid buffer solution was added. Then, with continued stirring, the solution was titrated with 0.00 IN iodine standard solution by monitoring millivolt changes with a redox electrode (platinum Ag/AgCl). The active chlorine concentration of the samples was then calculated from the following general formula (XX):
  • VI and V2 are the volumes (mL) of the iodine solution consumed in titrations of blank sodium thiosulfate solution and that with PET sample in, respectively.
  • N is the normality of iodine solution; and W is the weight of the samples in grams. This process was done for each final product to determine the active chlorine concentrations resulting from chlorination for both AS1 and NC2 samples.
  • FIG. 7 depicts the active chlorine concentration (ppm) compared with the various chlorination level of samples coated with the Coating Formulations 1, 2 and 3 and samples coated with the Coating Formulations 4 and 5.
  • the second and third data points are different from the first data point, labelled maximum chlorine potential at 1500 ppm.
  • the wash cycles were conducted according to AATCC 188-2010, "Colorfastness to Sodium Hypochlorite Bleach in Home Laundering."
  • the second and third data points may provide useful insight into the durability of the various coatings as well as a comparison to the theoretical maximum chlorine loading potential of each sample.
  • the chlorination uptake was also measured in the following examples of Coating Formulations 10 through 48.
  • Table 50 shows an example of idiometric titration data that reflects active-chlorine uptake of Coating Formulations 10 to 16 when coated on poly cotton and following exposure to 100 ppm chlorine for one hour of shaking.
  • Table 51 shows an example of idiometric titration data that reflects active-chlorine uptake of Coating Formulations 17 A, 18 and 19 when coated on poly cotton and following exposure to 100 ppm chlorine for 5 minutes of shaking. Table 51 Summary of chlorine uptake data for Coating Formulations 17A, 18 and 19.
  • Table 52 shows an example of idiometric titration data that reflects active-chlorine uptake of Coating Formulations 17 A, 18 and 19 when coated on polycotton and following exposure to 100 ppm chlorine for 60 minutes of shaking.
  • Table 53 shows an example of idiometric titration data that reflects active-chlorine uptake of Coating Formulations 20, 21 and 22 when coated on polycotton and following exposure to 100 ppm chlorine for 60 minutes of shaking.
  • Table 54 shows an example of idiometric titration data that reflects active-chlorine uptake of a virgin sample of polycotton that was exposed to 100 ppm for 60 minutes with wrist action shaking.
  • a solution of 25 mL 0.00 IN sodium thiosulfate and 30 mL of ultrapure water was prepared in a 100 mL beaker.
  • a magnetic stirring bar and one sample was added to each of the filled beakers. Each sample was stirred for a full hour before testing.
  • the burette was rinsed with iodine solution three times before use.
  • the burette was then filled with iodine solution and set up in a holder over the stirring base. While the samples were in the stirring process the titration control was performed.
  • a volumetric pipet was used to add the same volume of sodium thiosulfate solution as to what was used for the quenching of samples in a 100 mL beaker with 30 mL ultrapure water.
  • a small stirring bar was added to the beaker as was 2 mL a 5% acetic acid buffer and then stirring was commenced.
  • the electrode was set up erectly in the beaker and the start button on the conductivity/pH benchtop meter was pressed to electric potential mode (mV).
  • Iodine solution was added while observing the mV change shown on the pH meter.
  • Electric potential (mV) first decreased then increased with the addition of the iodine solution.
  • the endpoint of this titration is the point at which the electric potential shows a sudden jump. As for this titration the electric potential change is significant, so the mV change was used as the signal of endpoint. Record the ending reading in the burette.
  • AV in this process is just the VI in equation (2).
  • VI and V2 are the volumes (mL) of the iodine solution consumed in titrations of the sodium thiosulfate control and the chlorinated sample respectively.
  • N is the normality of iodine solution (eq. mol/L) and A is the surface area of the sample in cm 2 .
  • Table 55 shows an example of idiometric-titration data that reflects active-chlorine uptake of Coating Formulations 24, 26, 27, 28, 30, 31, 32 and 33 when coated on a hard, non- porous surface and following exposure to 100 ppm chlorine for 60 minutes of shaking.
  • Table 56 shows an example of idiometric-titration data that reflects active-chlorine uptake of Coating Formulations 35, 36, 37 and 38 when coated on a hard, non-porous surface and following exposure to 100 ppm chlorine for 60 minutes of shaking or an overnight soak in 100 ppm chlorine.
  • Table 57 shows an example of idiometric-titration data that reflects active-chlorine uptake of Coating Formulations 35, 37 and 38 when coated on to a hard, non-porous surface and following exposure to 200 ppm chlorine for 30 minutes of shaking.
  • Table 58 provides an example of idiometric-titration data that reflects active-chlorine uptake of Coating Formulation 40 and 41 when coated on a hard, non-porous surface and following exposure to 100 ppm chlorine for 10 minutes (Coating Formulation 41) or 60 minutes (Coating Formulation 40) of shaking. Table 58 Summary of chlorine uptake data for Coating Formulation 40 and 41.
  • FIG. 9 depicts the chlorination levels versus a number of wash cycles for the substrate sample that is coated with the AS1 and the substrate sample that is coated with the NC2 formulation.
  • the NCI coated substrate demonstrated a relatively stable chlorination propensity over the simulated life cycles.
  • the ASl samples demonstrated a degrading performance over more wash cycles. Chlorination was done after the wash cycles at 100 ppm, and neither of the samples was chlorinated prior to the wash cycles. This result is in line with expectations regarding the greater durability of the Coating Formulations 4 through 9 as compared with the Coating Formulations 1, 2 or 3.
  • Table 59 summarizes the active-chlorine content of a coated substrate that has been coated with Coating Formulation 10, 11, 12, 15 and 16 and then run through 0 or 50 cycles within laudrometer, as described above, followed by exposure to 100 ppm of chlorine for 60 minutes.
  • Table 60 summarizes the active-chlorine content of a coated substrate that has been coated with Coating Formulation 17A, 18, and 19 then run through 50 cycles within laudrometer, as described above, followed by exposure to 100 ppm of chlorine for 60 minutes.
  • DSC differential scanning calorimetry
  • Tg shift in which cured material is twice cycled through a ramp rate. The first provides a value for what the temperature of a glass-like state (Tg) the first cycle achieved. The second run indicates the ultimate Tg that could be achieved.
  • DSC data indicates that the polymer system of Coating Formulation 30
  • Biocidal Activity Assessment The biocidal properties of various of the Coated Samples were examined against clinical isolates of CA- Methicillin-resistant Staphylococcus aureus (MRSA) (#40065, community-associated,) and E. coli (ATCC 25922) using a "sandwich test" modified from AATCC 100 standard testing method.
  • Logarithmic-phase bacterial cultures were prepared by initially suspending several colonies in tap/hard water at a density equivalent to 0.5 McFarland standard of 10 8 colony -forming units (CFU)/mL, and then diluted 100 times to 10 6 CFU/mL. 20 ⁇ . of the diluted CA-MRSA and E.
  • the contact times for chlorinated samples were 1, 5, 10, 30 and 60 min, while for silver coated samples were 1, 2, 4 and 6 hours. Then, the samples were quenched with 5.0 mL of sterile 0.05M sodium thiosulfate solution to remove all oxidative chlorine, followed by 2 min of vortexing and 1 min of sonication. Serial dilutions of the solutions of vortexed and sonicated bacteria were made in tap/hard water, and they were plated on Tryptone Soya Agar. The plates were incubated at 37°C for 24 h, and viable bacterial colonies were recorded for bactericidal efficacy analysis.
  • N-chloramine treated fabric was also selected for assessing the biocidal activity. Due to its high absorbency and fluffy texture, it is difficult to fully extract bacterial cells from the Clorox sample in merely 5 mL of neutralizer (sodium thiosulfate) solution. Instead, the original AATCC 100 test method was used, where 1 mL of bacterial suspension (5 * 10 5 - ⁇ ⁇ ⁇ 6 CFU/mL) were completely absorbed by 2 pieces of square swatches l x l inch of N-chloramine treated fabrics (Clorox).
  • MRSA is one of the most frequently isolated organisms that contributes to healthcare associated infections (HAIs). Thus, it was selected to evaluate the biocidal activity of the coated substrates 12A along with the other commercially available modified textile products described above.
  • FIG. 10A and FIG. 10B depict the bacterial reduction (log) as a function of contact time between MRSA and the Coated Samples.
  • FIG. 10A and FIG. 10B represent the same data with different contact times (x-axis) provided.
  • line A represents Pristine Substrate
  • line B represents the AS 1 coated substrate sample
  • line C represents the NC2 coated substrate sample
  • line D represents the Clorox sample
  • line E represents the Under Armour sample
  • line F represents the Lululemon sample.
  • FIG. 10A and FIG. 10B show that both AS 1 and NC2 demonstrated a superior biocidal activity, arriving at a total killing of 5.70-log reduction of MRSA within 10 min.
  • the AS 1 -coated substrate had the fastest killing kinetics with 2.52-log reduction at 5 min.
  • a 1.03-log reduction was achieved by the NC2-coated fabric in 5 minutes.
  • the Clorox sample exhibited less efficient biocidal activity than both of the AS1 and
  • NC2 samples reaching a 1.67-log reduction at 10 min and killing substantially all the bacteria at 30 min.
  • concentration of active chlorine of the commercial N- chloramine treated fabric (Clorox) was 72 ppm, much lower than that of AS1 or NC2 coated samples, the antibacterial activity was still comparable.
  • AS1 and NCI regular N-chloramines
  • the dissimilar substrate of the commercial product may have contributed towards its performance.
  • the Clorox-treated substrate is very absorbent and quite fluffy, which may provide a substantial surface contact area for bacterial cells.
  • the ability to provide continued efficacy throughout the product life-cycle is one of the critical qualities of antimicrobial functionalized materials.
  • the laundry durability tests of the AS 1 and NC2 coated samples were conducted according to AATCC Test Method 61 (Test 2A Procedure). Washing cycles of 5, 25, 50, and 100 times were performed and then all the washed samples were then re-chlorinated at 100 ppm of chlorine. The antibacterial activities of the samples after different times of washing cycles were again evaluated against MRS A. As it can be seen in FIG. 11A and FIG.
  • FIG. 11B the slope of killing kinetics of the ASl coated samples decreased immediately after 5-time wash, arriving at 1.02-log and 2.58-log reduction at 5 min and 10 min, respectively, when compared to 2.52-log and 5.70-log reduction of unwashed ASl samples.
  • the disinfection curves of 5-, 25-, and 50-washed ASl samples were almost the same, achieving total kill at 30 min. Further increasing to 100-time wash resulted in a 1.67-log reduction at 10 min, slightly lower than the approximate 2.5-log reduction of the three washed samples.
  • FIG. 11A and FIG. 11B represent the same data with different contact times provided on the x-axis.
  • FIG. 12A and FIG. 12B represent the same data with different contact times provided on the x-axis.
  • FIG. 13 depicts the bacterial reduction (log) as a function of contact time between E. coli (ATCC 25922) and the Coated Samples.
  • line A represents the Pristine Substrate
  • line B represents the ASl coated substrate sample
  • line C represents the NC2 coated substrate sample
  • line D represents the Clorox sample
  • line E represents the Under Armour sample
  • line F represents the Lululemon sample.
  • ASl exhibited the fastest killing kinetics, arriving at 6.14-log reduction at 5 min, when compared to 1.96-log reduction of NC2 at 5 minutes.
  • the Pristine Substrate arrived at 1.79-log reduction after 6 hours.
  • the Under Armour sample showed minimal killing activity. It even demonstrated bacterial growth from 10 6 CFU/mL to 10 7 CFU/M1 after 6 hours.
  • Lululemon with X-static Silver technology demonstrated a total killing of 6.14-log reduction at 6 hours.
  • the Clorox sample demonstrated lower bacterial efficacy than ASl, arriving at 3.14-log reduction at 5 min, when compared to 6.14-log of ASl and 1.96-log of NC2.
  • biocidal activity of further coating formulations was tested when coated on both soft and hard substrates.
  • Table 61 shows a summary of biocidal activity of Coating Formulations 10, 11, 12, 15 and 16 when tested against Gram-positive MRS A bacteria.
  • Table 62 shows a summary of biocidal activity of Coating Formulations 17A and 18 when tested against gram positive MRSA bacteria. Table 62 Summary of Biocidal Activity of Coating Formulations 17A and 18.
  • Table 65 shows a summary of biocidal activity of Coating Formulations 35, 37 and 38 when tested against Gram-positive MRSA bacteria in a chlorinated and unchlorinated state.
  • Table 66 shows a summary of biocidal activity of Coating Formulation 40 when tested against Gram-positive MRSA bacteria in a chlorinated and unchlorinated state.
  • an article comprising a compound as described herein is contemplated.
  • Monomers or precursors and polymers of the monomers, precursors and compounds are also contemplated, and articles prepared from monomers, precursors and polymers thereof are also contemplated.
  • Methods of inactivating a microorganism or of inhibiting microbial growth are also contemplated.
  • a method comprising contacting the microorganism or a surface on which a microorganism resides with a compound, monomer of a compound, or an article coated with a compound or coating formulation as described herein is contemplated.
  • the microorganism can be a bacteria, a virus or a fungus.
  • a method whereby a compound or an article comprising a compound described herein is exposed to a source of chlorine, bromine or iodine.
  • a method is contemplated, wherein the method comprises providing a compound or an article comprising a compound described herein and exposing the compound or article comprising the compound to a source of chlorine, bromine or iodine.
  • the method finds use in rendering a surface aseptic or essentially aseptic.
  • the method also finds use in recharging biocidal activity of a compound or article coated with a compound or coating formulation as described herein.

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Abstract

La présente invention concerne un composé qui a une activité biocide ou qui est un précurseur d'un composé ayant une activité biocide. Le composé comprend un précurseur de N-halamine, au moins un ammonium quaternaire et au moins un groupe d'incorporation au revêtement (CIG). Dans certains modes de réalisation de la présente invention, le composé peut être incorporé dans une formulation de revêtement. La formulation de revêtement comprend ledit composé et au moins un autre constituant. Dans certains modes de réalisation de la présente invention, le CIG réagit avec l'autre constituant de la formulation de revêtement pour incorporer le composé dans la formulation de revêtement. Dans certains modes de réalisation, la formulation de revêtement comprend un polymère. Dans certains modes de réalisation, le CIG du composé réagit avec l'autre constituant pour incorporer le composé dans le polymère de la formulation de revêtement. La formulation de revêtement peut être utilisée pour revêtir un substrat. Le substrat revêtu peut démontrer une activité biocide ou le potentiel d'augmenter une activité biocide.
EP16854689.3A 2015-10-16 2016-10-14 Composés, polymères et formulations de revêtement comprenant au moins un précurseur de n-halamine, un centre cationique et un groupe d'incorporation au revêtement Withdrawn EP3362435A4 (fr)

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US201562269014P 2015-12-17 2015-12-17
US201662275534P 2016-01-06 2016-01-06
US201662287729P 2016-01-27 2016-01-27
US201662362460P 2016-07-14 2016-07-14
US201662393757P 2016-09-13 2016-09-13
PCT/CA2016/051200 WO2017063091A1 (fr) 2015-10-16 2016-10-14 Composés, polymères et formulations de revêtement comprenant au moins un précurseur de n-halamine, un centre cationique et un groupe d'incorporation au revêtement

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US10882822B2 (en) * 2016-07-06 2021-01-05 University Of Manitoba Use of compounds for making products with at least one N-halamine precursor group and at least one cationic center
CA3036484A1 (fr) * 2016-09-13 2018-03-22 Exigence Technologies Inc. Composes antimicrobiens ou precurseurs connexes comprenant un ou plusieurs centres cationiques et un groupe d'incorporation de revetement
WO2019023798A1 (fr) * 2017-07-31 2019-02-07 Exigence Technologies Inc. Composés polymérisables possédant une ou plusieurs propriétés de type tensioactif
CN115340629B (zh) * 2022-08-22 2023-07-07 东莞理工学院 季铵盐聚离子液体及使用季铵盐聚离子液体催化制备环状碳酸酯的方法

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US4073926A (en) * 1976-10-04 1978-02-14 Glyco Chemicals, Inc. Mono-quaternary ammonium salts of hydantoin and compositions thereof
US6768009B1 (en) * 2000-03-24 2004-07-27 The Regents Of The University Of California N-halamine vinyl compounds and their polymeric biocides
WO2003002652A1 (fr) * 2001-06-29 2003-01-09 Ciba Specialty Chemicals Holding Inc. Agents de remplissage organophiles nanometriques fonctionnalises par un additif
EP3357920A1 (fr) 2012-05-17 2018-08-08 Exigence Technologies Inc. Composés biocides et procédés d'utilisation associés
CA3001921C (fr) 2015-10-16 2021-04-27 Exigence Technologies Inc. Composes, polymeres et formulations de revetement comprenant au moins un precurseur de n-halamine, un centre cationique et un groupe d'incorporation au revetement
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US10882822B2 (en) * 2016-07-06 2021-01-05 University Of Manitoba Use of compounds for making products with at least one N-halamine precursor group and at least one cationic center

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US11059790B2 (en) 2015-10-16 2021-07-13 University Of Manitoba Compounds, polymers and coating formulations that comprise at least one N-halamine precursor, a cationic center and a coating incorporation group

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CA3001921A1 (fr) 2017-04-20
CN108602773B (zh) 2021-12-14
US20180297957A1 (en) 2018-10-18
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